US4344876A - Stabilization of acid catalyzed stoving lacquers - Google Patents

Stabilization of acid catalyzed stoving lacquers Download PDF

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US4344876A
US4344876A US06/211,480 US21148080A US4344876A US 4344876 A US4344876 A US 4344876A US 21148080 A US21148080 A US 21148080A US 4344876 A US4344876 A US 4344876A
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Godwin Berner
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C08K5/3435—Piperidines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/48—Stabilisers against degradation by oxygen, light or heat
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y10T428/31688—Next to aldehyde or ketone condensation product

Definitions

  • the present invention is concerned with the stabilising of acid catalysed stoving lacquers based on hot crosslinkable acrylic, polyester or alkyd resins against the action of light and moisture by the addition of N-substituted polyalkylpiperidine derivatives, and with the stabilised acid catalysed stoving varnishes thereby obtained.
  • the present invention relates to the use of N-substituted 2,2,6,6-tetraalkylpiperidine compounds, their acid addition salts or complexes with metal compounds, optionally together with further stabilisers for stabilising acid catalysed stoving lacquers based on hot crosslinkable acrylic, polyester or alkyd resins, in particular acrylic or alkyd resins, against the action of light, moisture and oxygen.
  • the eligible N-substituted 2,2,6,6-tetraalkylpiperidine compounds of the invention are generally known and are already in use to prevent degradation by light. They are for example compounds which contain a group of the formula (I) ##STR1## or polymers, the recurring structural units of which contain a group of the formula I or are linked through a bivalent group corresponding to the formula I, wherein R 1 represents a free valency, and otherwise R represents hydrogen or methyl and R 1 represents C 1 -C 18 alkyl, C 1 -C 6 hydroxyalkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C 7 -C 12 aralkyl which is unsubstituted or substituted in the alkyl moiety by hydroxyl, or C 1 -C 8 alkanoyl or C 3 -C 5 alkenoyl.
  • C 1 -C 12 alkyl is for example methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert.-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.
  • R 1 as C 1 -C 18 alkyl can be for example the groups recited above and in addition, for example, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.
  • R 1 as C 1 -C 6 hydroxyalkyl is in particular C 1 -C 4 -hydroxyalkyl and preferably 2-hydroxyethyl and 2-hydroxy-n-butyl.
  • R 1 as C 3 -C 8 alkenyl can be for example 1-propenyl, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-octenyl, 4-tert-butyl-2-butenyl.
  • R 1 as C 3 -C 8 alkinyl is preferably propargyl.
  • R 1 as C 7 -C 12 aralkyl is in particular phenethyl or, most preferably, benzyl, and, as aralkyl substituted in the alkyl moiety by hydroxyl, is in particular 2-hydroxyphenethyl.
  • R 1 as C 1 -C 8 alkanoyl is for example formyl, propionyl, butyryl, octanoyl, but preferably acetyl, and, as C 3 -C 5 alkenoyl, is in particular acryloyl.
  • R 2 as a monovalent radical of a carboxylic acid is for example a radical of acetic acid, stearic acid, salicylic acid, methacrylic acid, benzoic acid or ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid.
  • R 2 as a divalent radical of a dicarboxylic acid is for example a radical of maleic acid, adipic acid, suberic acid, sebacic acid, phthalic acid, dibutylmalonic acid, dibenzylmalonic acid or butyl-(3,5-di-tert-butyl-4-hydroxybenzyl)-malonic acid.
  • R 2 as a trivalent radical of a tricarboxylic acid is for example a trimellitic acid radical.
  • R 2 as a quadrivalent radical of a tetracarboxylic acid is for example a pyromellitic acid radical.
  • R 2 as a divalent radical of a dicarbamic acid is for example a hexamethylenedicarbamic acid radical or a 2,4-toluylenedicarbamic acid radical.
  • C 1 -C 12 alkyl are those already defined in (a) above.
  • C 5 -C 7 cycloalkyl is in particular cyclohexane.
  • R 3 as C 7 -C 8 aralkyl is in particular phenethyl or, most preferably, benzyl.
  • R 3 as C 2 -C 18 alkanoyl is for example propionyl, butyryl, octanoyl, dodecanoyl, hexadecanoyl, octadecanoyl, but preferably acetyl, and, as C 3 -C 5 alkenoyl, is in particular acryloyl.
  • R 4 as C 2 -C 8 alkenyl which is unsubstituted or substituted by a cyano, carbonyl or carbamide group is for example 1-propenyl, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-octenyl, 2,2-dicyanovinyl, 1-methyl-2-cyano-2-methoxycarbonylvinyl, 2,2-diacetylaminovinyl.
  • C 2 -C 12 alkylene is for example ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.
  • C 6 -C 15 arylene is for example o-, m- or p-phenylene 1,4-naphthylene or 4,4'-diphenylene.
  • X as C 6 -C 12 cycloalkylene is in particular cyclohexylene.
  • R 5 as C 2 -C 8 alkylene or hydroxyalkylene is for example ethylene, 1-methylethylene, propylene, 2-ethylpropylene, 2-ethyl-2-hydroxymethylpropylene.
  • R 5 as C 4 -C 22 acyloxyalkylene is for example 2-ethyl-2-acetoxymethylpropylene.
  • C 1 -C 12 alkyl is for example methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.
  • Z as C 1 -C 18 alkyl can be for example the groups cited above and, in addition, for example n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.
  • Substituents represented by C 2 -C 6 alkoxyalkyl are for example methoxymethyl, ethoxymethyl, propoxymethyl, tert-butoxymethyl, ethoxyethyl, ethoxypropyl, n-butoxyethyl, tert-butoxyethyl, isopropoxyethyl or propoxypropyl.
  • R 7 as C 3 -C 5 alkenyl is for example 1-propenyl, allyl, methallyl, 2-butenyl or 2-pentenyl.
  • R 7 as C 7 -C 9 aralkyl is in particular phenethyl or, most preferably, benzyl, and, as C 5 -C 7 cycloalkyl is in particular cyclohexyl.
  • R 7 as C 2 -C 4 hydroxyalkyl is for example 2-hydroxyethyl, 3-hydroxypropyl or 4-hydroxybutyl.
  • R 7 as C 6 -C 10 aryl is in particular phenyl, ⁇ - or ⁇ -naphthyl, which are unsubstituted or substituted by halogen or C 1 -C 4 alkyl.
  • R 7 as C 2 -C 12 alkylene is for example ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.
  • R 7 as C 6 -C 12 arylene is for example o-m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.
  • Z as C 2 -C 12 alkanoyl is for example propionyl, butyryl, octanoyl, dodecanoyl or preferably acetyl.
  • Substituents represented by C 1 -C 12 alkyl are for example methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.
  • Substituents represented by C 1 -C 4 hydroxyalkyl are for example ethylene, propylene, 2,2-dimethylpropylene, tetramethylene or hexamethylene.
  • R 11 and R 12 together as C 4 -C 5 alkylene or oxaalkylene are for example tetramethylene, pentamethylene or 3-oxa-pentamethylene.
  • Substituents represented by C 1 -C 12 alkyl are for example methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert.butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.
  • Substituents represented by C 1 -C 18 alkyl can be for example the groups cited above and, in addition, for example n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadeyl.
  • Groups represented by C 2 -C 10 alkylene are for example ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene or decamethylene.
  • R 14 as C 4 -C 18 alkyl is for example n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, 1,1-dimethyl-2-tert-butylethyl, n-nonyl, n-decyl, n-dodecyl, n-tridecyl, n-hexadecyl or n-octadecyl.
  • R 14 as C 1 -C 4 alkyl substituted by --CN is for example cyanomethyl, cyanoethyl, 3-cyano-n-propyl, 4-cyano-n-butyl.
  • R 14 as C 4 -C 12 alkylene is for example 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.
  • R 14 as C 7 -C 12 aralkyl is in particular phenethyl, p-methylbenzyl, or most preferable, benzyl.
  • R 15 as C 2 -C 4 alkenyl is for example vinyl, 1-propenyl, allyl, methallyl, 2-butenyl.
  • R 17 as C 2 -C 10 alkenyl represents for example the groups cited in the definition of R 15 as alkenyl and, in addition, for example crotyl, 2-hexenyl, 2-octenyl or 2-decenyl.
  • R 17 as C 6 -C 10 aryl is for example phenyl which is unsubstituted or substituted in the ortho- or para-position by methyl, ethyl, isopropyl, n-butyl or tert-butyl.
  • C 1 -C 18 Alkyl is, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl, or n-octadecyl.
  • C 7 -C 12 Aralkyl is, for example, phenylethyl or, in particular, benzyl.
  • R 1 as C 3 -C 8 alkenyl can be, for example, 1-propenyl, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-octenyl or 4-tert-butyl-2-butenyl.
  • R 1 as C 3 -C 8 alkynyl is preferably propargyl, and, as C 1 -C 8 -alkanoyl, is e.g. formyl, propionyl, butyryl, octanoyl, but preferably acetyl, and, as C 3 -C 5 alkenoyl, is in particular acryloyl.
  • R 3 as C 5 -C 7 cycloalkyl is in particular cyclohexyl, and, as C 6 -C 10 aryl, is in particular phenyl or ⁇ - or ⁇ -naphthyl, which can be substituted by halogen or C 1 -C 4 alkyl.
  • E as C 1 -C 3 alkylene is for example methylene, ethylene or propylene.
  • G as C 2 -C 6 alkylene is e.g. ethylene, propylene, 2,2-dimethylpropylene, tetramethylene or hexamethylene, and, as C 6 -C 12 arylene, is iso-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.
  • polyalkylpiperidine light stabilisers of this class are the compounds of the following formulae, wherein m is 2 to about 200: ##STR18## (i) Compounds which contain in their molecule at least one 2-(2'-hydroxyphenyl)-benztriazole group or 2-hydroxybenzophenone group and at least one polyalkylpiperidine group.
  • polyalkylpiperidine light stabilisers of this class are the compounds of the following formulae: ##STR19##
  • polyalkylpiperidine derivatives of classes (a) to (i) which form chemical bonds with the binder of the lacquer This occurs when the polyalkylpiperidine derivative contains a reactive group suitable for the purpose, for example a glycidyl group or a methylol group.
  • Examples of such compounds are the polyalkylpiperidine derivatives of class (g) which contain methylol or methylol ether groups.
  • the polyalkylpiperidine compounds are basic compounds, they can form salts with acids.
  • Suitable acids for the salt formation are for example inorganic acids or organic carboxylic, sulfonic, phosphonic or phosphinic acids, for example hydrochloric acid, boric acid, phosphoric acid, acetic acid, salicyclic acid, toluenesulfonic acid or benzenephpsphonic acid.
  • the polyalkylpiperidine compounds can form complexes with complex forming metal compounds, for example with zinc (II) acetate, cobalt(II) acetylacetonate, nickel(II) acetylacetonate, aluminium(III) acetylacetonate, nickel(II)benzoate or aluminium(III) benzoylacetonate.
  • complex forming metal compounds for example with zinc (II) acetate, cobalt(II) acetylacetonate, nickel(II) acetylacetonate, aluminium(III) acetylacetonate, nickel(II)benzoate or aluminium(III) benzoylacetonate.
  • the acrylic resin lacquers which can be stabilised against light, moisture and oxygen in accordance with the invention, are the conventional acrylic resin stoving lacquers which are described, for example, in H. Kittel's "Lehrbuch der Lacke und Be Anlagen für Heidelberg", Vol. 1, Part 2, on pages 735 and 742 (Berlin 1972), and in “Lackkunstharze” (1977), by H. Wagner and H. F. Sarx, on pages 229-238.
  • polyester lacquers which can be stabilised against the action of light and moisture, are the conventional stoving lacquers described e.g. in H. Wagner and H. F. Sarx, op. cit., on pages 86-99.
  • the alkyd resin lacquers which can be stabilised against the action of light and moisture in accordance with the invention are the conventional stoving lacquers which are used in particular for coating automobiles (automobile finishing lacquers), for example lacquers based on alkyd/melamine resins and alkyd/acrylic/melamine resins (see H. Wagner and H. F. Sarx, op. cit., pages 99-123).
  • the acid catalysed stoving lacquers stabilised in accordance with the invention are suitable both for metal finish coatings and solid shade finishes, especially in the case of retouching finishes.
  • the lacquers stabilised in accordance with the invention are preferably applied in the conventional manner by two methods, either by the single-coat method or by the two-coat method. In the latter method, the pigment-containing coat is applied first and then a covering coat of clear lacquer over it.
  • the amount of polyalkylpiperidine derivative employed is 0.01 to 5% by weight, based on the solvent-free binder, preferably 0.5 to 1% by weight.
  • the lacquers can be dissolved or dispersed in customary organic solvents or in water or can be solvent-free.
  • the polyalkylpiperidine derivative eligible for use in the inventive stabilising can be incorporated either only in the unpigmented finishing lacquer or both in the unpigmented finishing lacquer and in the pigmented priming lacquer.
  • polymerisable polyalkylpiperidine derivatives for example compounds 6 and 28
  • the incorporation into the lacquer binder can also, however, be effected via polycondensation in the manufacture or, as the case may be, in the stoving, of the melamine, alkyd or polyester resins.
  • polyalkylpiperidine derivatives which can be incorporated by condensation are compounds 1, 30 and 31, and also 1-hydroxyethyl-4-hydroxy-2,2,6,6-tetramethylpiperidine.
  • the incorporation via polyaddition can be accomplished for example via the reaction of free glycidyl groups in the polyalkylpiperidine derivative with acid groups of the acrylic resin. These glycidyl groups can be incorporated by polymerising (meth)acrylic acid into the resin.
  • UV absorbers of the benzophenone, benztriazole, acrylic acid derivative, or oxalanilide type UV absorbers of the benzophenone, benztriazole, acrylic acid derivative, or oxalanilide type, or metal-containing light stabilisers, for example organic nickel compounds.
  • the sum of all light stabilisers is 0.2 to 5% by weight, preferably 0.5 to 2% by weight, based on the film-forming resin.
  • antioxidants for example those of the sterically hindered phenol derivative type, phosphorus compounds, such as phosphites, phosphines or phosphonites, plasticisers, levelling assistants, hardening catalysts, thickeners, dispersants or adhesion promoters.
  • the priming lacquer was sprayed on to a thickness of about 15 ⁇ and aired for about 10 minutes. Then the clear lacquer was sprayed on to a thickness of about 30 ⁇ . After being aired for 15 minutes the samples were stoved for 30 minutes at 150° C.
  • Compound I 4-hydroxy-2,2,6,6-tetramethylpiperidine (N-unsubstituted homologue of compounds 1, 2, 3 and 4).
  • Compound II di-(2,2,6,6-tetramethylpiperidine-4-yl)-sebacate.
  • the coated sheets were subjected to weathering for 900 hours according to test method ASTM G-53/77 in a QUV tester.
  • ASTM G-53/77 in a QUV tester.
  • the samples were subjected to weathering for 4 hours in a humid atmosphere and UV light at 50° C. and for 4 hours under UV light at 60° C.
  • the weight loss of the finishes was determined gravimetrically (indicated in g/m 2 in column 2 of Table 1), and the gloss of the surface of the finish was measured in accordance with ASTM D 523 (the values are reported in column 3).
  • Example 3 To the priming lacquer described in Example 1 was added 0.34% of maleic acid (MA) and 0.071% of p-toluenesulfonic acid (pTS) as catalysts (percentage amounts, based in each case on the film-forming resin). After addition of 1% of the stabilisers listed in column 1 of Table 3, the lacquers were applied wet to glass plates in layers of about 50 ⁇ . The lacquers were then stoved for 30 minutes at 150° C. and, after storage for 1 day in an air-conditioned room (23° C./50% relative humidity), the hardness was evaluated by means of the oscillation test using the pendulum apparatus according to Konig (DIN 53 157). The results are reported in Table 3.
  • MA maleic acid
  • pTS p-toluenesulfonic acid
  • This lacquer has a content of 62.16% solids.
  • the following light stabilisers are added to this lacquer in the amounts given in table 5: ##STR21##
  • the lacquer was applied by spraying in such a thickness that after drying a coating of 30 ⁇ m resulted. After air-drying the samples were stoved for 30 minutes at 150° C.
  • N-unsubstituted piperidine light-stabiliser (A) effects a heavy delay in curing. If R 1 is methyl (B) or allyl (C) the delay becomes markedly smaller. In the case that R 1 is acetyl (D) no delay at all is to see.
  • R 1 is methyl (B) or allyl (C) the delay becomes markedly smaller.
  • R 1 is acetyl (D) no delay at all is to see.

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Abstract

Use of N-substituted 2,2,6,6-tetraalkylpiperidine compounds, their acid addition salts or complexes with metal compounds, optionally together with further stabilizers, for stabilizing acid catalyzed stoving lacquers based on hot cross-linkable acrylic or alkyd resins against the action of light, moisture and oxygen.

Description

This application is a continuation in part of copending application Ser. No. 047,407, filed June 11, 1979, now abandoned.
The present invention is concerned with the stabilising of acid catalysed stoving lacquers based on hot crosslinkable acrylic, polyester or alkyd resins against the action of light and moisture by the addition of N-substituted polyalkylpiperidine derivatives, and with the stabilised acid catalysed stoving varnishes thereby obtained.
On occasion, but especially in retouching finishes and lacquers with a high solids content for use in industrial finishes, stoving lacquer systems based on hot crosslinkable acrylic, polyester or alkyd resins are provided with an additional acid catalyst. In this case, failure symptoms caused by salt formation between light stabiliser and acid catalyst, delays in hardening, pigment flocculation, as well as a reduced light protective action, are observed. These problems can be solved in a satisfactory manner by means of the inventive use of N-substituted polyalkylpiperidine derivatives.
Accordingly, the present invention relates to the use of N-substituted 2,2,6,6-tetraalkylpiperidine compounds, their acid addition salts or complexes with metal compounds, optionally together with further stabilisers for stabilising acid catalysed stoving lacquers based on hot crosslinkable acrylic, polyester or alkyd resins, in particular acrylic or alkyd resins, against the action of light, moisture and oxygen.
The eligible N-substituted 2,2,6,6-tetraalkylpiperidine compounds of the invention are generally known and are already in use to prevent degradation by light. They are for example compounds which contain a group of the formula (I) ##STR1## or polymers, the recurring structural units of which contain a group of the formula I or are linked through a bivalent group corresponding to the formula I, wherein R1 represents a free valency, and otherwise R represents hydrogen or methyl and R1 represents C1 -C18 alkyl, C1 -C6 hydroxyalkyl, C3 -C8 alkenyl, C3 -C8 alkynyl, C7 -C12 aralkyl which is unsubstituted or substituted in the alkyl moiety by hydroxyl, or C1 -C8 alkanoyl or C3 -C5 alkenoyl.
Preferred N-substituted polyalkylpiperidine compounds are compounds or polymers which contain a group of the formula (I), wherein R is hydrogen and R1 represents C1 -C8 alkanoyl or C3 -C5 alkenoyl.
The following classes of compounds belong to the light stabilisers of the present invention:
(a) light stabilisers of the formula (II) ##STR2## wherein n is 1 to 4, preferably 1 or 2, R has the meaning given for the formula (I), R1 represents C1 -C18 alkyl, C1 -C6 hydroxyalkyl, C3 -C8 alkenyl, C3 -C8 alkynyl, C7 -C12 -aralkyl which is unsubstituted or substituted in the alkyl moiety by hydroxyl, or represents C1 -C8 alkanoyl or C3 -C5 alkenoyl, preferably C1 -C12 alkyl, allyl, benzyl, acetyl, acryloyl, and R2 if n is 1, represents hydrogen, C1 -C12 -alkyl, cyanoethyl, benzyl, glycidyl, a monovalent radical of a saturated or unsaturated aliphatic, cycloaliphatic, araliphatic or aromatic carboxylic acid, carbamic acid or phosphorus-containing acid or a monovalent silyl radical, preferably a radical of an aliphatic carboxylic acid containing 2 to 18 carbon atoms, of a cycloaliphatic carboxylic acid containing 5 to 12 carbon atoms or of an aromatic carboxylic acid containing 7 to 15 carbon atoms, and if n is 2, represents C1 -C12 alkylene, C4 -C12 alkenylene, xylylene, a divalent radical of a saturated or unsaturated aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acid, dicarbamic acid or phosphorus-containing acid or a divalent silyl radical, preferably a radical of an aliphatic dicarboxylic acid containing 2 to 12 carbon atoms, a cycloaliphatic or aromatic dicarboxylic acid containing 8 to 14 carbon atoms, or of an aliphatic, cycloaliphatic or aromatic dicarbamic acid containing 8 to 14 carbon atoms, and, if n is 3, represents a trivalent radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid, of an aromatic tricarbamic acid or of a phosphorus-containing acid or a trivalent silyl radical, and if n is 4, represents a quadrivalent radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid.
C1 -C12 alkyl is for example methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert.-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.
R1 as C1 -C18 alkyl can be for example the groups recited above and in addition, for example, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.
R1 as C1 -C6 hydroxyalkyl is in particular C1 -C4 -hydroxyalkyl and preferably 2-hydroxyethyl and 2-hydroxy-n-butyl.
R1 as C3 -C8 alkenyl can be for example 1-propenyl, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-octenyl, 4-tert-butyl-2-butenyl.
R1 as C3 -C8 alkinyl is preferably propargyl.
R1 as C7 -C12 aralkyl is in particular phenethyl or, most preferably, benzyl, and, as aralkyl substituted in the alkyl moiety by hydroxyl, is in particular 2-hydroxyphenethyl.
R1 as C1 -C8 alkanoyl is for example formyl, propionyl, butyryl, octanoyl, but preferably acetyl, and, as C3 -C5 alkenoyl, is in particular acryloyl.
R2 as a monovalent radical of a carboxylic acid is for example a radical of acetic acid, stearic acid, salicylic acid, methacrylic acid, benzoic acid or β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid.
R2 as a divalent radical of a dicarboxylic acid is for example a radical of maleic acid, adipic acid, suberic acid, sebacic acid, phthalic acid, dibutylmalonic acid, dibenzylmalonic acid or butyl-(3,5-di-tert-butyl-4-hydroxybenzyl)-malonic acid.
R2 as a trivalent radical of a tricarboxylic acid is for example a trimellitic acid radical.
R2 as a quadrivalent radical of a tetracarboxylic acid is for example a pyromellitic acid radical.
R2 as a divalent radical of a dicarbamic acid is for example a hexamethylenedicarbamic acid radical or a 2,4-toluylenedicarbamic acid radical.
The following compounds are examples of polyalkylpiperidine light stabilisers of this class:
1--4-hydroxy-1,2,2,6,6-pentamethylpiperidine
2--1-allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine
3--1-benzyl-4-hydroxy-2,2,6,6-tetramethylpiperidine
4--1-(4-tert-butyl-2-butenyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine
5--1-ethyl-4-salicyloyloxy-2,2,6,6-tetramethylpiperidine
6--4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine
7--1,2,2,6,6-pentamethylpiperidin-4-yl-β-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propionate
8--1-benzyl-2,2,6,6-tetramethyl-4-piperidinylmaleinate
9--di-(1,2,3,6-tetramethyl-2,6-diethyl-piperidin-4-yl)-sebacate
10--di-(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacate
11--di-(1-allyl-2,2,6,6-tetramethylpiperidin-4-yl)-sebacate
12--di-(1-allyl-2,2,6,6-tetramethyl-piperidin-4-yl)phthalate
13--di-(1,2,2,6,6-pentamethylpiperidin-4-yl)-adipate
14--di-(1-allyl-2,2,6,6-tetramethylpiperidin-4-yl)adipate
15--1-propargyl-4-β-cyanoethyloxy-2,2,6,6-tetramethyl-piperidine
16--1-acetyl-2,2,6,6-tetramethylpiperidin-4-yl-acetate
17--1-acryloyl-4-benzyloxy-2,2,6,6-tetramethylpiperidine
18--dibutyl-di-(1,2,2,6,6-pentamethylpiperidin-4-yl)-malonate
19--butyl-(3,5-di-tert-butyl-4-hydroxybenzyl)-di-(1,2,2,6,6-pentamethylpiperidin-4-yl)-malonate
20--dibenzyl-di-(1,2,2,6,6-pentamethyl-piperidin-4-yl)-malonate
21--dibenzyl-di-(1,2,3,6-tetramethyl-2,6-diethylpiperidin-4-yl)-malonate
22--hexan-1',6'-bis-(4-carbamoyloxy-1-n-butyl-2,2,6,6-tetramethylpiperidine)
23---toluene-2',4'-bis-(4-carbamoyloxy-1-n-propyl-2,2,6,6-tetramethylpiperidine)
24--tris-(1-propyl-2,2,6,6-tetramethylpiperidin-4-yl)-phosphite
25--tris-(1-propyl-2,2,6,6-tetramethylpiperidin-4-yl-phosphate
26--phenyl-[bis-(1,2,2,6,6-pentamethylpiperidin-4-yl)]-phosphonate
(b) Light stabilisers of the formula (III) ##STR3## wherein n is 1 or 2, R has the meaning given for formula (I), R1 has the meaning given in (a) above, R3 represents C1 -C12 alkyl, C5 -C7 cycloalkyl, C7 -C8 aralkyl, C2 -C18 alkanoyl, C3 -C5 alkenoyl, or benzoyl, and R4 if n is 1, represents C1 -C12 alkyl, C5 -C7 cycloalkyl, C2 -C8 alkenyl which is unsubstituted or substituted by a cyano, carbonyl or carbamide group, glycidyl, a group of the formula --CH2 --CH(OH)--Z or of the formula --CONH--Z, wherein Z is hydrogen, methyl or phenyl, and, if n is 2, represents C2 -C12 alkylene, C6 -C12 arylene, xylylene, a --CH2 CH(OH)--CH2 group or a --CH2 --CH(OH)--CH2 --O--X--O--CH2 --CH(OH)--CH2 group, wherein X represents C2 -C10 alkylene, C6 -C15 arylene, C6 -C12 cycloalkylene, or, with the proviso that R3 does not represent alkynoyl, alkenoyl or benzoyl, R4 can also represent a divalent radical of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid or dicarbamic acid, or R3 and R4 together, if n is 1, can be the cyclic radical of an aliphatic or aromatic 1,2- or 1,3-dicarboxylic acid.
Substituents represented by C1 -C12 alkyl are those already defined in (a) above. C5 -C7 cycloalkyl is in particular cyclohexane. R3 as C7 -C8 aralkyl is in particular phenethyl or, most preferably, benzyl. R3 as C2 -C18 alkanoyl is for example propionyl, butyryl, octanoyl, dodecanoyl, hexadecanoyl, octadecanoyl, but preferably acetyl, and, as C3 -C5 alkenoyl, is in particular acryloyl.
R4 as C2 -C8 alkenyl which is unsubstituted or substituted by a cyano, carbonyl or carbamide group is for example 1-propenyl, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-octenyl, 2,2-dicyanovinyl, 1-methyl-2-cyano-2-methoxycarbonylvinyl, 2,2-diacetylaminovinyl.
C2 -C12 alkylene is for example ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.
C6 -C15 arylene is for example o-, m- or p-phenylene 1,4-naphthylene or 4,4'-diphenylene.
X as C6 -C12 cycloalkylene is in particular cyclohexylene.
The following compounds are examples of polyalkylpiperidine light stabilisers of this class:
27--N,N'-bis-(1,2,2,6,6-pentamethylpiperidin-4-yl)hexamethylene-1,6-diacetamide
28--1-acetyl-4-(N-cyclohexylacetamido)-2,2,6,6-tetramethylpiperidine
29--The compound of the formula ##STR4## 30--4-(di-2-hydroxyethyl)-amino-1,2,2,6,6-pentamethylpiperidine 31--4-(di-2-hydroxyethyl)-amino-1-(2-hydroxyethyl)-2,2,6,6-tetramethylpiperidine
32--4-methacrylamido-1,2,2,6,6-pentamethylpiperidine
(c) Light stabilisers of the formula (IV) ##STR5## wherein n is 1 or 2, R has the meaning given for formula (I) R1 has the meaning given in (a), and R5 if n is 1, represents C2 -C8 alkylene or hydroxyalkylene or C4 -C22 acyloxyalkylene, and if n is 2, represents the group (--CH2)2 C(CH2 --)2.
R5 as C2 -C8 alkylene or hydroxyalkylene is for example ethylene, 1-methylethylene, propylene, 2-ethylpropylene, 2-ethyl-2-hydroxymethylpropylene.
R5 as C4 -C22 acyloxyalkylene is for example 2-ethyl-2-acetoxymethylpropylene.
The following compounds are examples of polyalkylpiperidine light stabilisers of this class:
33--8-aza-2,7,7,8,9,9-hexamethyl-1,4-dioxyspiro[4.5]decane
34--9-aza-3-hydroxymethyl-3-ethyl-8,8,9,10,10-pentamethyl-1,5-dioxaspiro[5.5]undecane
35--9-aza-3-ethyl-3-acetoxymethyl-9-acetyl-8,8,10,10-tetramethyl-1,5-dioxaspiro[5.5]undecane
(d) Light stabilisers of the formula (V) ##STR6## wherein n is 1 or 2, R has the meaning given for formula (I), R1 has the meaning given in (a), R6 represents hydrogen, C1 -C12 alkyl, allyl, benzyl, glycidyl, C2 -C6 alkoxyalkyl, and R7 if n is 1, represents hydrogen, C1 -C12 alkyl, glycidyl, C3 -C5 alkenyl, C7 -C9 aralkyl, C5 -C7 cycloalkyl, C2 -C4 hydroxyalkyl, C2 -C6 alkoxyalkyl, C6 -C10 aryl, and if n is 2, represents C2 -C12 alkylene, C6 -C12 arylene or a group --CH2 CH(OZ)CH2 --(OCH2 --CH(OZ)CH2)2 --, wherein Z represents hydrogen, C1 -C18 alkyl, allyl, benzyl, C2 -C12 alkanoyl or benzoyl.
C1 -C12 alkyl is for example methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.
Z as C1 -C18 alkyl can be for example the groups cited above and, in addition, for example n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.
Substituents represented by C2 -C6 alkoxyalkyl are for example methoxymethyl, ethoxymethyl, propoxymethyl, tert-butoxymethyl, ethoxyethyl, ethoxypropyl, n-butoxyethyl, tert-butoxyethyl, isopropoxyethyl or propoxypropyl.
R7 as C3 -C5 alkenyl is for example 1-propenyl, allyl, methallyl, 2-butenyl or 2-pentenyl.
R7 as C7 -C9 aralkyl is in particular phenethyl or, most preferably, benzyl, and, as C5 -C7 cycloalkyl is in particular cyclohexyl.
R7 as C2 -C4 hydroxyalkyl is for example 2-hydroxyethyl, 3-hydroxypropyl or 4-hydroxybutyl.
R7 as C6 -C10 aryl is in particular phenyl, α- or β-naphthyl, which are unsubstituted or substituted by halogen or C1 -C4 alkyl.
R7 as C2 -C12 alkylene is for example ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.
R7 as C6 -C12 arylene is for example o-m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.
Z as C2 -C12 alkanoyl is for example propionyl, butyryl, octanoyl, dodecanoyl or preferably acetyl.
The following compounds are examples of polyalkylpiperidine light stabilisers of this class:
36--3-benzyl-1,3,8-triaza-7,7,8,9,9-pentamethylspiro[4.5]decane-2,4-dione
37--3-n-octyl-1,3,8-triaza-7,7,8,9,9-pentamethylspiro[4.5]decane-2,4-dione
38--3-allyl-1,3,8-triaza-1,7,7,8,9,9-hexamethylspiro[4.5]decane-2,4-dione
or the compounds of the following formulae: ##STR7## (e) Light stabilisers of the formula (VI) ##STR8## wherein n is 1 or 2, R8 represents a group of the formula ##STR9## wherein R has the meaning given for formula (I), R1 has the meaning given in (a), Y is --O-- or --NR11, A represents C2 -C6 alkylene and m is 0 or 1, R9 represents the groups R8, NR11 R12, --OR13, --NHCH2 OR13 or --N(CH2 OR13)2, R10 if n is 1, represents the groups R8 or R9 and, if n is 2, represents the group --Y--Q--Y--, wherein Q represents C2 -C6 alkylene which is optionally interrupted by --N(R14)--, R11 represents C1 -C12 alkyl, cyclohexyl, benzyl or C1 -C4 hydroxyalkyl or a group of the formula ##STR10## R12 represents C1 -C12 alkyl, cyclohexyl, benzyl, C1 -C4 hydroxyalkyl, R13 represents hydrogen, C1 -C12 alkyl or phenyl, and R14 represents hydrogen or the group --CH2 OR13, or R11 and R12 together are C4 -C5 alkylene or oxaalkylene, or each of R11 and R12 represents a group of the formula ##STR11##
Substituents represented by C1 -C12 alkyl are for example methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.
Substituents represented by C1 -C4 hydroxyalkyl are for example ethylene, propylene, 2,2-dimethylpropylene, tetramethylene or hexamethylene.
R11 and R12 together as C4 -C5 alkylene or oxaalkylene are for example tetramethylene, pentamethylene or 3-oxa-pentamethylene.
Compounds of the following formulae are examples of polyalkylpiperidine light stabilisers of this class: ##STR12## (f) Light stabilisers of the formula (VII) ##STR13## wherein n is 1 or 2, R represents hydrogen or methyl, and R14 if n is 1, represents C4 -C18 alkyl, C7 -C12 aralkyl, the group --CO--R15, C1 -C4 alkyl substituted by --CN, --COOR16, --OH, --OCOR17 or ##STR14## wherein R15 represents C1 -C12 alkyl, C2 -C4 alkenyl or phenyl, R16 represents C1 -C18 alkyl, R17 represents C1 -C18 alkyl, C2 -C10 alkenyl, cyclohexyl, benzyl or C6 -C10 aryl or R14, if n is 2, represents C4 -C12 alkylene, 2-butenylene-1,4, xylylene, the groups --(CH2)2 --OOC--R18 --COO--(CH2)2 --, --CH2 --OOC--R19 --COO--CH2 -- or --CH2 --CH(OH)--CH2 --O--R18 --O--CH2 --CH(OH)--CH2 --, wherein R18 represents C2 -C10 alkylene, phenylene, cyclohexylene or 2,2-diphenylenepropane, and R19 represents C2 -C10 alkylene, xylylene or cyclohexylene.
Substituents represented by C1 -C12 alkyl are for example methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert.butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.
Substituents represented by C1 -C18 alkyl can be for example the groups cited above and, in addition, for example n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadeyl.
Groups represented by C2 -C10 alkylene are for example ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene or decamethylene.
R14 as C4 -C18 alkyl is for example n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, 1,1-dimethyl-2-tert-butylethyl, n-nonyl, n-decyl, n-dodecyl, n-tridecyl, n-hexadecyl or n-octadecyl.
R14 as C1 -C4 alkyl substituted by --CN is for example cyanomethyl, cyanoethyl, 3-cyano-n-propyl, 4-cyano-n-butyl.
R14 as C4 -C12 alkylene is for example 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.
R14 as C7 -C12 aralkyl is in particular phenethyl, p-methylbenzyl, or most preferable, benzyl.
R15 as C2 -C4 alkenyl is for example vinyl, 1-propenyl, allyl, methallyl, 2-butenyl.
R17 as C2 -C10 alkenyl represents for example the groups cited in the definition of R15 as alkenyl and, in addition, for example crotyl, 2-hexenyl, 2-octenyl or 2-decenyl.
R17 as C6 -C10 aryl is for example phenyl which is unsubstituted or substituted in the ortho- or para-position by methyl, ethyl, isopropyl, n-butyl or tert-butyl.
The following compounds are examples of polyalkylpiperidine light stabilisers of this class:
45--bis-[2-(2,2,6,6-tetramethylpiperidino)-ethyl]sebacate
46--1-octoxycarbonylmethyl-2,2,6,6-tetramethylpiperidine
47--1,4-bis-(2,2,6,6-tetramethylpiperidino)-2-butene.
(g) Light stabilisers of the formula (VIII) ##STR15## wherein Q is --N(R3)-- or --O--, E is C1 -C3 alkylene, the --CH2 --CH(R4)--O-- group, wherein R4 is hydrogen, methyl or phenyl, the --(CH2)3 --NH-- group or a single bond, R is hydrogen or methyl, R1 is C1 -C18 alkyl, C3 -C8 alkenyl, C3 -C8 alkynyl, C7 -C12 aralkyl, C1 -C8 alkanoyl, C3 -C5 alkenoyl, glycidyl, R2 is hydrogen or C1 -C18 alkyl, R3 is hydrogen, C1 -C18 alkyl, C5 -C7 cycloalkyl, C7 -C12 aralkyl, cyanoethyl, C6 -C10 aryl, the --CH2 --CH(R4)--OH group, wherein R4 is as defined above, a group of the formula ##STR16## or a group of the formula ##STR17## wherein G can be C2 -C6 alkylene or C6 -C12 arylene, or R3 is a E--CO--NH--CH2 --OR2 group.
C1 -C18 Alkyl is, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl, or n-octadecyl.
C7 -C12 Aralkyl is, for example, phenylethyl or, in particular, benzyl.
R1 as C3 -C8 alkenyl can be, for example, 1-propenyl, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-octenyl or 4-tert-butyl-2-butenyl.
R1 as C3 -C8 alkynyl is preferably propargyl, and, as C1 -C8 -alkanoyl, is e.g. formyl, propionyl, butyryl, octanoyl, but preferably acetyl, and, as C3 -C5 alkenoyl, is in particular acryloyl.
R3 as C5 -C7 cycloalkyl is in particular cyclohexyl, and, as C6 -C10 aryl, is in particular phenyl or α- or β-naphthyl, which can be substituted by halogen or C1 -C4 alkyl. E as C1 -C3 alkylene is for example methylene, ethylene or propylene.
G as C2 -C6 alkylene is e.g. ethylene, propylene, 2,2-dimethylpropylene, tetramethylene or hexamethylene, and, as C6 -C12 arylene, is iso-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.
The following compounds are examples of polyalkylpiperidine light stabilisers of this class:
48--N-hydroxymethyl-N'-2,2,6,6-tetramethylpiperidine-4-yl urea
49--N-methoxymethyl-N'-2,2,6,6-tetramethylpiperidin-4-yl urea
50--N-methoxymethyl-N'-n-dodecyl-N'-2,2,6,6-tetramethylpiperidin-4-yl urea
51--O-(2,2,6,6-tetramethylpiperidin-4-yl)-N-methoxymethyl urea.
(h) Polymeric compounds, the recurring structural units of which contain a group of the formula I or which are linked through a bivalent group corresponding to the formula I, wherein R1 represents a free valency, and otherwise R and R1 have the meanings given above, especially polyesters, polyethers, polyamides, polyamines, polyurethanes, polyureas, polyaminotriazines, poly(meth)acrylates, poly(meth)acrylamides and the copolymers thereof which contain such radicals.
Examples of polyalkylpiperidine light stabilisers of this class are the compounds of the following formulae, wherein m is 2 to about 200: ##STR18## (i) Compounds which contain in their molecule at least one 2-(2'-hydroxyphenyl)-benztriazole group or 2-hydroxybenzophenone group and at least one polyalkylpiperidine group.
Examples of polyalkylpiperidine light stabilisers of this class are the compounds of the following formulae: ##STR19##
It is also possible to use polyalkylpiperidine derivatives of classes (a) to (i) which form chemical bonds with the binder of the lacquer. This occurs when the polyalkylpiperidine derivative contains a reactive group suitable for the purpose, for example a glycidyl group or a methylol group.
Examples of such compounds are the polyalkylpiperidine derivatives of class (g) which contain methylol or methylol ether groups.
If the polyalkylpiperidine compounds are basic compounds, they can form salts with acids. Suitable acids for the salt formation are for example inorganic acids or organic carboxylic, sulfonic, phosphonic or phosphinic acids, for example hydrochloric acid, boric acid, phosphoric acid, acetic acid, salicyclic acid, toluenesulfonic acid or benzenephpsphonic acid.
The polyalkylpiperidine compounds can form complexes with complex forming metal compounds, for example with zinc (II) acetate, cobalt(II) acetylacetonate, nickel(II) acetylacetonate, aluminium(III) acetylacetonate, nickel(II)benzoate or aluminium(III) benzoylacetonate.
The acrylic resin lacquers, which can be stabilised against light, moisture and oxygen in accordance with the invention, are the conventional acrylic resin stoving lacquers which are described, for example, in H. Kittel's "Lehrbuch der Lacke und Beschichtungen", Vol. 1, Part 2, on pages 735 and 742 (Berlin 1972), and in "Lackkunstharze" (1977), by H. Wagner and H. F. Sarx, on pages 229-238.
The polyester lacquers, which can be stabilised against the action of light and moisture, are the conventional stoving lacquers described e.g. in H. Wagner and H. F. Sarx, op. cit., on pages 86-99.
The alkyd resin lacquers which can be stabilised against the action of light and moisture in accordance with the invention, are the conventional stoving lacquers which are used in particular for coating automobiles (automobile finishing lacquers), for example lacquers based on alkyd/melamine resins and alkyd/acrylic/melamine resins (see H. Wagner and H. F. Sarx, op. cit., pages 99-123).
The acid catalysed stoving lacquers stabilised in accordance with the invention are suitable both for metal finish coatings and solid shade finishes, especially in the case of retouching finishes. The lacquers stabilised in accordance with the invention are preferably applied in the conventional manner by two methods, either by the single-coat method or by the two-coat method. In the latter method, the pigment-containing coat is applied first and then a covering coat of clear lacquer over it.
The amount of polyalkylpiperidine derivative employed is 0.01 to 5% by weight, based on the solvent-free binder, preferably 0.5 to 1% by weight. The lacquers can be dissolved or dispersed in customary organic solvents or in water or can be solvent-free.
When used in two-coat finishes, the polyalkylpiperidine derivative eligible for use in the inventive stabilising can be incorporated either only in the unpigmented finishing lacquer or both in the unpigmented finishing lacquer and in the pigmented priming lacquer. In the manufacture of acrylic modified alkyd resins or acrylic resins, polymerisable polyalkylpiperidine derivatives (for example compounds 6 and 28) can be polymerised into the resin. The incorporation into the lacquer binder can also, however, be effected via polycondensation in the manufacture or, as the case may be, in the stoving, of the melamine, alkyd or polyester resins.
Examples of polyalkylpiperidine derivatives which can be incorporated by condensation are compounds 1, 30 and 31, and also 1-hydroxyethyl-4-hydroxy-2,2,6,6-tetramethylpiperidine. The incorporation via polyaddition can be accomplished for example via the reaction of free glycidyl groups in the polyalkylpiperidine derivative with acid groups of the acrylic resin. These glycidyl groups can be incorporated by polymerising (meth)acrylic acid into the resin.
In these cases, there is the additional advantage that the light stabilisers cannot be removed by extraction or migration, so that their action is very prolonged.
To attain maximum light stability, the concurrent use of other conventional light stabilisers can be advantageous. Examples are UV absorbers of the benzophenone, benztriazole, acrylic acid derivative, or oxalanilide type, or metal-containing light stabilisers, for example organic nickel compounds.
If such combinations are employed, the sum of all light stabilisers is 0.2 to 5% by weight, preferably 0.5 to 2% by weight, based on the film-forming resin.
Further ingredients which the lacquers can contain are antioxidants, for example those of the sterically hindered phenol derivative type, phosphorus compounds, such as phosphites, phosphines or phosphonites, plasticisers, levelling assistants, hardening catalysts, thickeners, dispersants or adhesion promoters.
The following Examples describe the inventive use of N-substituted polyalkylpiperidine derivatives in acid catalysed stoving lacquers based on acrylic resin containing binder systems. Parts and percentages are by weight.
EXAMPLE 1 Stabilising action of different polyalkylpiperidine derivatives in a hot crosslinkable acrylic resin lacquer catalysed with maleic acid (two-coat metallic effect finish) Basic composition of the lacquers (a) Metallic effect priming lacquer
27 parts of polyester resin L 1850 (Dynamit Nobel AG)
3 parts of melamine resin Maprenal RT (Farbwerke Hoechst AG)
2 parts of cellulose acetobutyrate CAB 531 (Eastman Chem. Corp.)
8 parts of aluminium bronze ALCOA 726 (aluminium Corp. of America)
10 parts of toluene
7 parts of xylene
3 parts of butanol
25 parts of butyl acetate
15 parts of aromatic solvent Solvesso 150 (Esso AG).
(b) Unpigmented finishing lacquer
56 parts of acrylic resin Paraloid OL 42 (Rohm & Haas Corp.)
20 parts of melamine resin Cymel 301 (American Cyanimide Corp.)
3.5 parts of maleic acid (20% in dioxan)
2 parts of cellulose acetobutyrate CAB 551 (Eastman Chem. Corp.)
11 parts of butanol
4.5 parts of butyl acetate.
Pieces of aluminium sheeting measuring 57×79 mm×0.5 mm, which were coated with a primer based on polyester/epoxide resin, were first coated with the priming lacquer and subsequently with the finishing lacquer. The priming lacquer was sprayed on to a thickness of about 15μ and aired for about 10 minutes. Then the clear lacquer was sprayed on to a thickness of about 30μ. After being aired for 15 minutes the samples were stoved for 30 minutes at 150° C.
Before application, 1% (based on the film-forming resin) of the polyalkylpiperidine compound listed in column 1 of Table 1 was added to the priming lacquer in each case (numbered according to the Examples referred to the description). For comparison, the following N-unsubstituted polyalkylpiperidine compounds designated by Roman numerals were also employed:
Compound I: 4-hydroxy-2,2,6,6-tetramethylpiperidine (N-unsubstituted homologue of compounds 1, 2, 3 and 4).
Compound II: di-(2,2,6,6-tetramethylpiperidine-4-yl)-sebacate.
Compound III: ##STR20##
After storage for 4 weeks in an air-conditioned room (23° C./50% relative humidity), the coated sheets were subjected to weathering for 900 hours according to test method ASTM G-53/77 in a QUV tester. In this test, the samples were subjected to weathering for 4 hours in a humid atmosphere and UV light at 50° C. and for 4 hours under UV light at 60° C. Subsequently the weight loss of the finishes was determined gravimetrically (indicated in g/m2 in column 2 of Table 1), and the gloss of the surface of the finish was measured in accordance with ASTM D 523 (the values are reported in column 3).
              TABLE 1                                                     
______________________________________                                    
Stabiliser   Weight loss                                                  
                       20° gloss (averaged)                        
______________________________________                                    
without additive                                                          
             21.8      5                                                  
compound I   6.5       14                                                 
compound II  16.4      4                                                  
compound III 19.9      3                                                  
compound 1   6.6       66                                                 
compound 2   6.9       67                                                 
compound 3   6.8       72                                                 
compound 4   6.8       48                                                 
compound 20  5.7       55                                                 
compound 31  9.0       36                                                 
compound 58  8.9       37                                                 
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EXAMPLE 2 Precipitations in an acid-catalysed, hot crosslinkable acrylic resin lacquer
Each of the light stabilisers listed in column 1 of Table 2 (1% based on the coating) was dissolved in the priming lacquer described in Example 1, initially without addition of catalyst. Then maleic acid was added as catalyst in the same amount as indicated in Example 1, and precipitation effects were observed, depending on the type of stabiliser employed. The results are reported in Table 2.
              TABLE 2                                                     
______________________________________                                    
         Appearance of the lacquer                                        
Stabiliser without addition of acid                                       
                           with addition of acid                          
______________________________________                                    
without addition                                                          
           clear           clear                                          
compound I clear           precipitate                                    
compound II                                                               
           clear           precipitate                                    
compound III                                                              
           clear           precipitate                                    
compound 1 clear           clear                                          
compound 2 clear           clear                                          
compound 3 clear           clear                                          
compound 4 clear           clear                                          
compound 19                                                               
           clear           clear                                          
compound 20                                                               
           clear           clear                                          
compound 31                                                               
           clear           clear                                          
compound 45                                                               
           clear           clear                                          
compound 58                                                               
           clear           clear                                          
______________________________________
EXAMPLE 3 Delays in curing by addition of light stabilisers to acid-catalysed hot crosslinkable acrylic resin lacquers
To the priming lacquer described in Example 1 was added 0.34% of maleic acid (MA) and 0.071% of p-toluenesulfonic acid (pTS) as catalysts (percentage amounts, based in each case on the film-forming resin). After addition of 1% of the stabilisers listed in column 1 of Table 3, the lacquers were applied wet to glass plates in layers of about 50μ. The lacquers were then stoved for 30 minutes at 150° C. and, after storage for 1 day in an air-conditioned room (23° C./50% relative humidity), the hardness was evaluated by means of the oscillation test using the pendulum apparatus according to Konig (DIN 53 157). The results are reported in Table 3.
              TABLE 3                                                     
______________________________________                                    
Stabiliser     0.34% MA  0.071% pTS                                       
______________________________________                                    
without addition                                                          
               148       164                                              
compound II     76       tacky                                            
compound III   113       tacky                                            
compound 2     142       166                                              
compound 3     140       162                                              
compound 4     145       158                                              
compound 19    138        83                                              
compound 20    152        57                                              
compound 45    131       142                                              
compound 58    145       162                                              
______________________________________
EXAMPLE 4 Influence of polyalkylpiperidine derivatives on spraying in an acid-catalysed stoving lacquer (single-coat metallic effect finish) Basic composition of the lacquer
57.6 parts of acrylic resin lacquer Synthracryl SC 300 (Farbwerke Hoechst), 50% in xylene/butanol 2:1
24.5 parts of melamine resin Maprenal MF 650 (Farbwerke Hoechst), 55% in isobutanol
1.3 parts of aluminium paste Stapa Mobile R (Eckast-Werke, Furth, Germany)
3.4 parts of maleic acid (20% in dioxane)
3.9 parts butyl glycol acetate
2 parts of ethyl glycol acetate
7.3 parts of xylene.
The metallic effect lacquer was adjusted with xylene to a spray viscosity of about 19 sec (DIN 53211) and sprayed onto aluminium sheets coated with a coil coat. After brief airing, the finishes were stoved for 30 minutes at 80° C. and evaluated. The results are reported in Table 4 (compounds I, II and III: cf. Example 1. The light stabilisers of the invention are numbered according to the Examples referred to in the description).
              TABLE 4                                                     
______________________________________                                    
Light stabiliser*  Appearance of the finishes                             
(1%, based on lacquer solids)                                             
                   after stoving                                          
______________________________________                                    
without additive   faultless                                              
compound I         pitting, spreading                                     
                   faults                                                 
compound II        dull, pitting                                          
compound III       dull, pitting                                          
compound 1         faultless                                              
compound 2         faultless                                              
compound 3         faultless                                              
compound 19        faultless                                              
______________________________________                                    
 *dissolved in xylene and then added to the lacquer
EXAMPLE 5 Delays in low-temperature curing by addition of piperidine light stabilisers
Aluminium sheets of 0.5 mm thickness, coated with a white primer based on a polyester resin, were coated with a high-solid clear lacquer of the following recipe:
53.7 parts acrylic resin (Paraloid OL 42, Rohm & Haas Corp.)
19.3 parts melamine resin (Cymel 301, Amer. Cyanamid Corp.)
3.0 parts cellulose acetobutyrate (CAB 551, Eastman Chem. Corp.)
10.5 parts n-butanol
10.5 parts butyl acetate
3.0 parts flow control agent (Byketol special, Byk-Mallinckrodt)
0.12 parts p-toluenesulfonic acid
This lacquer has a content of 62.16% solids. The following light stabilisers are added to this lacquer in the amounts given in table 5: ##STR21##
The lacquer was applied by spraying in such a thickness that after drying a coating of 30 μm resulted. After air-drying the samples were stoved for 30 minutes at 150° C.
After storage for 30 minutes in an air-conditioned room (23° C./50% rel. humidity) the hardness of the coating films was evaluated by the pendulum method of Koenig (DIN 53 157). The resulting "pendulum hardness" is listed in table 5.
              TABLE 5                                                     
______________________________________                                    
Light Stabiliser                                                          
              Pendulum Hardness (sec)                                     
______________________________________                                    
without       60                                                          
0.5% LS A     tacky                                                       
0.5% LS B     20                                                          
0.5% LS C     24                                                          
0.5% LS D     60                                                          
______________________________________
It is to see from the table that the N-unsubstituted piperidine light-stabiliser (A) effects a heavy delay in curing. If R1 is methyl (B) or allyl (C) the delay becomes markedly smaller. In the case that R1 is acetyl (D) no delay at all is to see. Such more detailled differences between the N-substituted piperidine derivatives of the invention becomes evident in the case of lower curing temperatures and of lower catalyst concentration. Therefore for retouching lacquers the N-acylated compounds are the preferred light stabilisers of the invention.

Claims (19)

What is claimed is:
1. A composition of matter consisting of an acid-catalysed stoving lacquer based on hot crosslinkable acrylic, polyester or alkyd resins and stabilised with a N-substituted 2,2,6,6-tetraalkylpiperidine compound or its acid addition salt.
2. A composition according to claim 1 which contains a compound which contains a group of the formula (I) ##STR22## or which contains a polymer, the recurring structural units of which contain a group of the formula (I) or are linked through a bivalent group corresponding to the formula I, wherein R1 represents a free valency, and otherwise R represents hydrogen or methyl and R1 represents C1 -C18 alkyl, C1 -C6 hydroxyalkyl, C3 -C8 alkenyl, C3 -C8 alkynyl, C7 -C12 aralkyl which is unsubstituted or substituted in the alkyl moiety by hydroxyl, or C1 -C8 alkanoyl or C3 -C5 alkenoyl.
3. A composition according to claim 1 which contains a compound or a polymer which contains a group of the formula (I) wherein R is hydrogen and R1 represents C1 -C8 alkanoyl or C3 -C5 alkenoyl.
4. A composition according to claim 3, wherein R1 is acetyl.
5. A composition according to claim 2 which contains a light stabiliser of the formula (II) ##STR23## wherein n is 1 to 4, R is hydrogen or methyl, R1 represents C1 -C18 alkyl, C1 -C6 hydroxyalkyl, C3 -C8 alkenyl, C3 -C8 alkynyl, C7 -C12 aralkyl which is unsubstituted or substituted in the alkyl moiety by hydroxyl, or represents C1 -C8 alkanoyl or C3 -C5 alkenoyl, R2 if n is 1, represents hydrogen, C1 -C12 alkyl, cyanoethyl, glycidyl, benzyl, a monovalent radical of a saturated or unsaturated aliphatic, cycloaliphatic or aromatic carboxylic acid, carbamic acid or phosphorus-containing acid or a monovalent silyl radical, and if n is 2, represents C1 -C12 alkylene, C4 -C12 alkenylene, xylylene, a divalent radical of a saturated or unsaturated aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acid, dicarbamic acid or phosphorus-containing acid or a divalent silyl radical, and, if n is 3, represents a trivalent radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid, of an aromatic tricarbamic acid or of a phosphorus-containing acid or a trivalent silyl radical, and, if n is 4, represents a quadrivalent radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid.
6. A composition according to claim 4 which contains a light stabiliser of the formula (II), wherein n is 1 or 2, R is hydrogen or methyl, R1 is C1 -C12 alkyl, allyl, benzyl, acetyl, acryloyl, and R2 if n is 1, represents a radical of an aliphatic carboxylic acid of 2 to 18 carbon atoms, of a cycloaliphatic carboxylic acid of 5 to 12 carbon atoms or of an aromatic carboxylic acid of 7 to 15 carbon atoms, and if n is 2, represents a radical of an aliphatic dicarboxylic acid of 2 to 12 carbon atoms, of a cycloaliphatic or aromatic dicarboxylic acid of 8 to 14 carbon atoms, of an aliphatic, cycloaliphatic or aromatic dicarbamic acid of 8 to 14 carbon atoms.
7. A composition according to claim 2 which contains a light stabiliser of the formula (III) ##STR24## wherein n is 1 or 2, R is hydrogen or methyl, R1 represents C1 -C18 alkyl, C1 -C6 hydroxyalkyl, C3 -C8 alkenyl, C3 -C8 alkynyl, C7 -C12 aralkyl which is unsubstituted or substituted in the alkyl moiety by hydroxyl, or represents C1 -C8 alkanoyl or C3 -C5 alkenoyl, R3 represents C1 -C12 alkyl, C5 -C7 cycloalkyl, C7 -C8 aralkyl, C2 -C18 alkanoyl, C3 -C5 alkenoyl, or benzoyl, and R4 if n is 1, represents C1 -C12 alkyl, C5 -C7 cycloalkyl, C2 -C8 alkenyl which is unsubstituted or substituted by a cyano, carbonyl or carbamide group, glycidyl, a group of the formula --CH2 CH(OH)--Z or of the formula --CONH--Z, wherein Z is hydrogen, methyl or phenyl, and, if n is 2, represents C2 -C12 alkylene, C6 -C12 arylene, xylylene, a --CH2 --CH(OH)--CH2 -- group or a --CH2 --CH(OH)--CH2 --O--X--O--CH2 --CH(OH)--CH2 -- group, wherein X represents C2 -C10 alkylene, C6 -C15 arylene, C6 -C12 -cycloalkylene, or, with the proviso that R3 does not represent alkanoyl, alkenoyl or benzoyl, R4 can also represent a divalent radical of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid or dicarbamic acid, or R3 and R4 together, if n is 1, can be the cyclic radical of an aliphatic or aromatic 1,2- or 1,3-dicarboxylic acid.
8. A composition according to claim 2 which contains a light stabiliser of the formula (IV) ##STR25## wherein n is 1 or 2, R is hydrogen or methyl, R1 represents C1 -C18 alkyl, C1 -C6 hydroxyalkyl, C3 -C8 alkenyl, C3 -C8 alkynyl, C7 -C12 aralkyl which is unsubstituted or substituted in the alkyl moiety by hydroxyl, or represents C1 -C8 alkanoyl or C3 -C5 alkenoyl, R5 if n is 1, represents C2 -C8 alkylene or hydroxyalkylene or C4 -C22 acyloxyalkylene, and if n is 2, represents the group (--CH2)2 C(CH2 --)2.
9. A composition according to claim 2 which contains a light stabiliser of the formula (V) ##STR26## wherein n is 1 or 2, R is hydrogen or methyl, R1 represents C1 -C18 alkyl, C1 -C6 hydroxyalkyl, C3 -C8 alkenyl, C3 -C8 alkynyl, C7 -C12 aralkyl which is unsubstituted or substituted in the alkyl moiety by hydroxyl, or represents C1 -C8 alkanoyl or C3 -C5 alkenoyl, R6 represents hydrogen, C1 -C12 alkyl, allyl, benzyl, glycidyl, C2 -C6 alkoxyalkyl, and R7 if n is 1, represents hydrogen, C1 -C12 alkyl, glycidyl, C3 -C5 alkenyl, C7 -C9 aralkyl, C5 -C7 cycloalkyl, C2 -C4 hydroxyalkyl, C2 -C6 alkoxyalkyl, C6 -C10 aryl, and, if n is 2, represents C2 -C12 alkylene, C6 -C12 arylene or a group --CH2 CH(OZ)CH2 --(OCH.sub. 2 --CH(OZ)CH2)2 --, wherein Z represents hydrogen, C1 -C18 alkyl, allyl, benzyl, C2 -C12 alkanoyl or benzoyl.
10. A composition according to claim 2 which contains a light stabiliser of the formula (VI) ##STR27## wherein n is 1 or 2 and R8 represents a group of the formula ##STR28## wherein R is hydrogen or methyl, R1 represents C1 -C18 alkyl, C1 -C6 hydroxyalkyl, C3 -C8 alkenyl, C3 -C8 alkynyl, C7 -C12 aralkyl which is unsubstituted or substituted in the alkyl moiety by hydroxyl, or represents C1 -C8 alkanoyl or C3 -C5 alkenoyl, Y represents --O-- or NR11, A represents C2 -C6 alkylene, m is 0 or 1, R9 represents the groups R8, NR11 R12, --OR12, --NHCH2 OR13 or --N(CH2 OR13)2, R10 if n is 1, represents the groups R8 or R9 and, if n is 2, represents the group --Y--Q--Y--, wherein Q represents C2 -C6 alkylene which is optionally interrupted by --N(R14)--, R11 represents C1 -C12 alkyl, cyclohexyl, benzyl or C1 -C4 hydroxyalkyl or a group of the formula ##STR29## R12 represents C1 -C12 alkyl, cyclohexyl, benzyl, C1 -C4 hydroxyalkyl, R13 represents hydrogen, C1 -C12 alkyl or phenyl, and R14 represents hydrogen or the group --CH2 OR13, or R11 and R12 together are C4 -C5 alkylene or oxaalkylene, or each of R11 and R12 also represents a group of the formula ##STR30##
11. A composition according to claim 1 which contains a light stabiliser of the formula (VII) ##STR31## wherein n is 1 or 2, R represents hydrogen or methyl, and R14 if n is 1, represents C4 -C18 alkyl, C7 -C12 aralkyl, the group --CO--R15, C1 -C4 alkyl substituted by --CN, --COOR16, --OH, --OCOR17, or ##STR32## and R15 represents C1 -C12 alkyl, C2 -C4 alkenyl or phenyl, R16 represents C1 -C18 alkyl, R17 represents C1 -C18 alkyl, C2 -C10 alkenyl, cyclohexyl, benzyl or C6 -C10 aryl, or R14, if n is 2, represents C4 -C12 alkylene, 2-butenylene-1,4, xylylene, the groups --(CH2)2 --OOC--R18 --COO--(CH2)2 --, --CH2 --OOC--R19 --COO--CH2 -- or --CH2 --CH(OH)--CH2 --O--R18 --O--CH2 --CH(OH)--CH2 --, wherein R18 represents C2 -C10 alkylene, phenylene, cyclohexylene or 2,2-diphenylenepropane, and R19 represents C2 -C10 alkylene, xylylene or cyclohexylene.
12. A composition according to claim 2 which contains a light stabiliser of the formula (VIII) ##STR33## wherein Q is --N(R3)-- or --O--, E is C1 -C3 alkylene, the --CH2 --CH(R4)--O-- group, wherein R4 is hydrogen, methyl or phenyl, the --(CH2)3 NH-- group or a single bond, R is hydrogen or methyl, R1 is C1 -C18 alkyl, C3 -C8 alkenyl, C3 -C8 alkynyl, C7 -C12 aralkyl, C1 -C8 alkanoyl, C3 -C5 alkenoyl or glycidyl, R2 is hydrogen or C1 -C18 alkyl, R3 is hydrogen, C1 -C18 alkyl, C5 -C7 cycloalkyl, C7 -C12 aralkyl, cyanoethyl, C6 -C10 aryl, the --CH2 --CH(R4)--OH group, wherein R4 is as defined above, a group of the formula ##STR34## or a group of the formula ##STR35## wherein G can be C2 -C6 alkylene or C6 -C12 arylene, or R3 is a E--CO--NH--CH2 --OR2 group.
13. A composition according to claim 2, which contains polymeric compounds as light stabilisers, the recurring structural units of which contain a group of the formula I or are linked through a bivalent group corresponding to the formula I, wherein R1 represents a free valency, and otherwise R and R1 have the meanings given in claim 2, in particular polyesters, polyethers, polyamides, polyamines, polyurethanes, polyureas, polyaminotriazines, poly(meth)acrylates, poly(meth)acrylamides and the copolymers thereof, which contain such radicals.
14. A composition according to claim 1, which contains an acid addition salt of a N-substituted 2,2,6,6-tetraalkylpiperidine compound.
15. A composition according to claim 1, wherein the N-substituted 2,2,6,6-tetraalkylpiperidine compound is contained in an amount of 0.1 to 5% by weight, based on the solvent-free binder (film-forming resin).
16. A composition according to claim 1, which contains additionally a UV absorber of the benzophenone, benzotriazole, acrylic acid derivative or oxalanilide type.
17. A composition according to claim 1, which additionally contains antioxidants, plasticisers, levelling agents, hardening catalysts, thickeners, dispersants or adhesion promoters.
18. A composition according to claim 1, which is a lacquer of high solids content for industrial finishes.
19. A composition according to claim 1 which is a retouching lacquer for automobiles.
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US4426471A (en) 1984-01-17
EP0006213A1 (en) 1980-01-09
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EP0006213B1 (en) 1982-09-01
JPH0233736B2 (en) 1990-07-30

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